Electron spin resonance and electron nuclear double resonance of photogenerated polarons in polyfluorene and its fullerene composite

Electron spin resonance (ESR) and electron-nuclear double resonance (ENDOR) of photogenerated polarons in poly(9,9-dioctylfluorene) (PFO) and its composite with fullerene (C60) using variable photoexcitation energy up to 4.1 eV are reported. For PFO, a light-induced ESR (LESR) signal (g=2.003) is observed below 60 K, and its transient response and excitation spectrum indicate that the observed spins are photogenerated polarons on PFO. For the PFO-C60 composite, two LESR signals of photogenerated positive polarons on PFO (g1=2.003) and radical anions on C60 (g2=1.999), respectively, are observed below 120 K, which are caused by photoinduced electron transfer from PFO to C60. A remarkable enhancement of the LESR signals in the excitation spectrum at ~2.8 eV is observed compared with the case of pure PFO. The bimolecular-recombination kinetics of photogenerated charge carriers in the composite are confirmed by the dependence of the LESR on excitation-light intensity and by the decay dynamics. Light-induced ENDOR (LENDOR) signals are clearly observed for excitation around 2.8 eV owing to the highly efficient photoinduced electron transfer in the composite. Broad LENDOR shifts directly reflect the spin-density distribution of the polarons in PFO. We have determined its maximum shift using LENDOR-induced ESR, and have evaluated the maximum spin density on the carbon site coupled to the proton as 0.032. This value is consistent with the theoretical result obtained by Pariser-Parr-Pople (PPP) model, where the spatial extent of the polarons is calculated as ~3 monomer units of PFO. The calculated LESR spectra of PFO based on the PPP model are consistent with the experimental spectra, which confirm the above spatial extension of the polaron in PFO